Abstract
The development of degradable polymers has commanded significant attention over the past half century. Approaches have predominantly relied on ring-opening polymerization of cyclic esters (e.g., lactones, lactides) and N-carboxyanhydrides, as well as radical ring-opening polymerizations of cyclic ketene acetals. In recent years, there has been a significant effort applied to expand the family of degradable polymers accessible via olefin metathesis polymerization. Given the excellent functional group tolerance of olefin metathesis polymerization reactions generally, a broad range of conceivable degradable moieties can be incorporated into appropriate monomers and thus into polymer backbones. This approach has proven particularly versatile in synthesizing a broad spectrum of degradable polymers including poly(ester), poly(amino acid), poly(acetal), poly(carbonate), poly(phosphoester), poly(phosphoramidate), poly(enol ether), poly(azobenzene), poly(disulfide), poly(sulfonate ester), poly(silyl ether), and poly(oxazinone) among others. In this review, we will highlight the main olefin metathesis polymerization strategies that have been used to access degradable polymers, including (i) acyclic diene metathesis polymerization, (ii) entropy-driven and (iii) enthalpy-driven ring-opening metathesis polymerization, as well as (iv) cascade enyne metathesis polymerization. In addition, the livingness or control of polymerization reactions via different strategies are highlighted and compared. Potential applications, challenges and future perspectives of this new library of degradable polyolefins are discussed. It is clear from recent and accelerating developments in this field that olefin metathesis polymerization represents a powerful synthetic tool towards degradable polymers with novel structures and properties inaccessible by other polymerization approaches.